WO1997027001A1 - Passivation composition and process for coating - Google Patents
Passivation composition and process for coating Download PDFInfo
- Publication number
- WO1997027001A1 WO1997027001A1 PCT/US1997/000012 US9700012W WO9727001A1 WO 1997027001 A1 WO1997027001 A1 WO 1997027001A1 US 9700012 W US9700012 W US 9700012W WO 9727001 A1 WO9727001 A1 WO 9727001A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- amount
- molybdenum
- dissolved
- components
- ratio
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims description 47
- 238000000576 coating method Methods 0.000 title claims description 21
- 239000011248 coating agent Substances 0.000 title claims description 20
- 238000002161 passivation Methods 0.000 title abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 44
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 28
- 239000011733 molybdenum Substances 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 56
- 239000003638 chemical reducing agent Substances 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 29
- 239000012141 concentrate Substances 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- -1 phosphate anions Chemical class 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims 14
- 229920000058 polyacrylate Polymers 0.000 claims 2
- 239000006185 dispersion Substances 0.000 claims 1
- 235000016768 molybdenum Nutrition 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 14
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000011282 treatment Methods 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 235000008504 concentrate Nutrition 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 229940124024 weight reducing agent Drugs 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 7
- 239000000470 constituent Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- NSMXQKNUPPXBRG-SECBINFHSA-N (R)-lisofylline Chemical compound O=C1N(CCCC[C@H](O)C)C(=O)N(C)C2=C1N(C)C=N2 NSMXQKNUPPXBRG-SECBINFHSA-N 0.000 description 1
- 229910000680 Aluminized steel Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-M hydroxylamine;chloride Chemical compound [Cl-].ON WTDHULULXKLSOZ-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CAKRAHQRJGUPIG-UHFFFAOYSA-M sodium;[4-azaniumyl-1-hydroxy-1-[hydroxy(oxido)phosphoryl]butyl]-hydroxyphosphinate Chemical compound [Na+].NCCCC(O)(P(O)(O)=O)P(O)([O-])=O CAKRAHQRJGUPIG-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/342—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more reactive oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/00525—Coating or impregnation materials for metallic surfaces
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1075—Chromium-free or very low chromium-content materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
Definitions
- This invention relates to compositions and processes for passivating, i.e., forming a corrosion protective surface layer, on metal surfaces that consist predominantly of aluminum and/or zinc.
- a wide variety of such surfaces are in normal use, including many kinds of galvanized and/or aluminized steel, and the invention is applicable to such surfaces which differ from the underlying metal, as well as to solid alloys of aluminum and/or zinc.
- the invention is particularly advantageous for use on a surface of 55 % aluminum, 43.5 % aluminum, and 1.5 % Si that is often itself used as a coating on underlying steel.
- (C) a dissolved, stably dispersed, or both dissolved and stably dispersed component selected from the group consisting of reducing agents, non-molybdenum-con- taining products from reactions in which the reducing agents reduce other materi ⁇ al, or both, said reducing agents and products from reactions thereof not being part of either of previously recited components (A) and (B);
- (F) recited above means that the insoluble component is not spontaneously concentrated into any separate liquid or solid phase perceptible with unaided human vision as distinct from, but in contact with, the liquid continuous phase within a period of observation of the combination of stably dispersed insoluble component and liquid continuous phase for 10 hours, or preferably, with increasing preference in the order given, for 1, 3, 5, 10, 30, 60, 90, 120, 240, or 360 days.
- Various embodiments of the invention include working compositions for direct use in treating metals, make-up concentrates from which such working compositions can be prepared by dilution with water, replenisher concentrates suitable for maintaining op ⁇ timum performance of working compositions according to the invention, processes for treating metals with a composition according to the invention, and extended processes including additional steps that are conventional per se, such as cleaning, rinsing, and sub ⁇ sequent painting or some similar overcoating process that puts into place an organic bind ⁇ er-containing protective coating over the metal surface treated according to a narrower embodiment of the invention.
- Articles of manufacture including surfaces treated accord- ing to a process of the invention are also within the scope of the invention. Description of Preferred Embodiments
- compositions according to the invention as defined above should be substantially free from many ingredients used in compositions for similar purposes in the prior art.
- these compositions contain no more than 25, 15, 9, 5, 3, 1.0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01, 0.001, or 0.0002, percent of each of the following constituents: nitrite; halates and perhalates (i.e., perchlorate, chlorate, iodate, etc.); hydroxylamine and salts and complex ⁇ es of hydroxylamine; chloride; bromide; iodide; organic compounds containing nitro groups; hexavalent chromium; ferricyanide; ferrocyanide; and pyrazole compounds.
- the dissolved phosphate ions that constitute necessary component (A) may be ob ⁇ tained from a variety of sources as known in the art. Normally much of the phosphate ion content will be supplied by phosphoric acid added to the composition, and the stoi ⁇ chiometric equivalent as phosphate ions of all undissociated phosphoric acid and all its anionic ionization products in solution, along with the stoichiometric equivalent as phos ⁇ phate ions of any dihydrogen phosphate, monohydrogen phosphate, or completely neu- tralized phosphate ions added to the composition in salt form, are to be understood as forming part of phosphate ions component (A), irrespective of the actual degree of ioni ⁇ zation and/or reaction to produce some other chemical species that exists in the composition.
- component (A) If any metaphosphoric acid, other condensed phosphoric acids, or salts of any of these acids are present in the compositions, their stoichiometric equivalent as phosphate is also considered part of component (A). Generally, however, it is preferred, at least partly for reasons of economy, to utilize orthophosphoric acid and its salts as the initial source for component (A).
- the concentration of phosphate ions and/or their stoichiometric equivalents as noted above preferably is at least, with increasing preference in the order given, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 10.5, 11.0, 11.5, 12.0, or 12.2 grams per liter (hereinafter usu ⁇ ally abbreviated as "g/L") of total composition and independently preferably is not more than, with increasing preference in the order given, 200, 100, 80, 70, 65, 60, 55, 50, 46, 43, 40, 30, 27, 24, 21, 19, 17, 15, or 13 g/L.
- the dissolved and/or dispersed substance(s) which contain molybdenum in a val ⁇ ence state lower than +6 and constitute the second necessary component of a working passivating aqueous liquid composition according to the invention are preferably, at least in part for reasons of economy, provided by in situ reaction between molybdenum triox ⁇ ide (in which molybdenum has the +6 valence state) and a reducing agent in the presence of water and phosphate ions, preferably, in order to complete the reaction within a rea ⁇ sonable time, at a temperature well above normal ambient temperature.
- This reaction preferably is caused to occur in a mixture which comprises, more preferably consists es- sentially of, or still more preferably consists of, water, molybdenum trioxide, orthophos ⁇ phoric acid, and reducing agent and which is suitable for use, after this reaction, as a make-up concentrate composition according to the invention that, when diluted with wat- er only, supplies all of components (A), (B), (C), and (D) as defined above that are need ⁇ ed in a working passivating aqueous liquid composition according to the invention.
- the amount of molybdenum trioxide used preferably is at least, with increasing preference in the order given, 20, 40, 60, 70, 80, 85, 90, 95, 100, 105, 108, 1 1 1, or 1 13 grams per kilogram of the total amount of material mixed (hereinafter usually abbreviated as "g/kg") and independently preferably is not more than, with increasing preference in the order given, 400, 350, 300, 250, 200, 175, 155, 140, 130, 125, 120, or 115 g/kg; (ii) independently, the amount of phosphate ions used preferably is at least, with increasing preference in the order given, 20, 40, 60, 70, 75, 80, 85, 90, 95, or 100 g/kg and independently preferably is not more than, with in ⁇ creasing preference in the order given, 700, 600, 550, 500, 475, 450.
- the amount of reducing agent used preferably is at least, with increasing preference in the order given, 2, 4, 6, 8, 10, 12, 14, 16, 18, 30.
- 50, 70, or 90 g/kg and independently preferably is not more than, with increasing preference in the order given, 200, 175, 150, 125, or 100 g/kg; (iv) all other ingredients constitute ⁇ he balance of the material mixed to form the concentrate make-up composition; and (v) independently, the ratio of the amount of molybdenum trioxide to the amount of phosphate ions mixed to prepare the concentrate make-up composition is at least 0.20:1.0, 0.30:1.0, 0.35:1.0, 0.45:1.0, 0.65:1.0, 0.75:1.0, 0.85:1.0, 0.95:1.0, or 1.05: 1.0 and independently preferably is, with increasing preference in the order given, not more than 4.0:1.0, 3.5: 1.0, 3.0: 1.0, 2.5: 1.0, 2.0: 1.0, 1.5: 1.0.
- the reduc- ing agent added initially preferably is selected from the group consisting of organic com ⁇ pounds in which the ratio of oxygen atoms to carbon atoms is at least, with increasing preference in the order given, 0.3 : 1.0, 0.6: 1.0, 0.7: 1.0, or 0.8: 1.0 and independently pref- erably is not more than, with increasing preference in the order given, 1.5: 1.0, 1.3:1.0, or 1.1 : 1.0.
- the reducing agent is pref ⁇ erably selected from substances containing no atoms other than carbon, oxygen, and hy ⁇ drogen, and most preferably is starch.
- the reducing agent used it preferably is sufficiently effective as a reducing agent and is used in a sufficient amount to react with the preferred amounts of molybdenum trioxide as given above in the presence of water and the preferred amounts of phosphoric acid as given above to convert the entire amount of molybdenum trioxide used into one or more soluble and/or stably dispersed molybdenum-containing substances, in which at least part of the molybdenum is in a val- ence state lower than +6.
- the amount of molybdenum that is in a valence state lower than +6 in a composi ⁇ tion according to the invention may be and preferably is measured by titration of a samp ⁇ le of the composition with potassium permanganate solution to a color change from blue or green to yellow, orange, or brown. This method indicates that not nearly all of the total dissolved and/or stably dispersed molybdenum atoms in most preferred concentrate make-up compositions according to the invention are in a lower valence state.
- At least one of optional components (E) and (F) should be present in at least working compositions according to the invention, because the presence of at least one of these components normally increases the corrosion protec ⁇ tion and/or the resistance to discoloration of the passivated surface formed.
- Normally fluoride-containing component (E) is more preferred than component (F), particularly when selected from the group consisting of fluozirconic acid, fluotitanic acid, fluosilicic acid, fluoboric acid, and the salts of all these acids. Fluozirconic acid and its salts are most preferred.
- the total concentration of fluorine atoms in anions in component (E) preferably is at least, with increasing preference in the order given, 0.02, 0.04, 0.06, 0.08, 0.10, 0.15, 0.20, 0.22, or 0.24 g/L and independently preferably is, primarily for reasons of economy, not more than, with increasing preference in the order given, 2.0, 1.5, 1.0, 0.80, 0.70, 0.60, 0.50, 0.45, 0.40, 0.35, 0.30, 0.28, or 0.26 g/L.
- component (F) is present in a working or a concentrate passivating aqueous li ⁇ quid composition according to the invention, it is preferably selected from silica and/or alumina in colloidally dispersed form.
- Surfactant component (G) is not normally needed, but in some cases may be ad ⁇ vantageous to promote thorough and uniform wetting of the surface to be passivated.
- a working passivating aqueous liquid composition according to the invention preferably has a pH value that is not more than, with increasing preference in the order given, 5, 3, 2.5, 2.2, 1.9, or 1.7 and independently preferably is at least, with increasing preference in the order given, -1.0, -0.5, 0.0, 0.5, 0.70, 0.80. 0.85, 0.90, 0.95, or 1.0.
- a process according to the invention in its simplest form consists of bringing a o metal surface to be passivated into physical contact with a working composition accord ⁇ ing to the invention as described above for a period of time, then discontinuing such con ⁇ tact and drying the surface previously contacted.
- Physical contact and subsequent sepa ⁇ ration can be accomplished by any of the methods well known in the metal treatment art, such as immersion for a certain time, then discontinuing immersion and removing adher- 5 ent liquid by drainage under the influence of natural gravity or with a squeegee or similar device; spraying to establish the contact, then discontinuing the spraying and removing excess liquid as when contact is by immersion; roll coating of the amount of liquid followed by drying into place, and the like.
- the temperature of the working passivating aqueous liquid composition o during a passivation process according to the invention is at least, with increasing prefer ⁇ ence in the order given, 15, 20, 25, 30, 34 or 37 °C and independently preferably, prof ⁇ ily for reasons of economy, is not more than 66, 60, 55, or 50 °C.
- the quality of the pas- sivation layer formed is not known to be substantially affected by the temperature during passivating if the temperature is within any of these preferred limis; the primary reason for the preference for a minimum temperature during passivating that is greater than the normal ambient temperature is that with such a passivating temperature and squeegeeing 5 off of any adherent liquid promptly after discontinuing contact of the surface to be passivated with a working passivating aqueous liquid composition according to the invention, the surface will dry spontaneously in ambient air within a few seconds to form a passivated surface according to the invention. This method of operation is particularly well adapted to most existing coil processing plants.
- the time during which physical contact is maintained between the metal surface to be passivated and a working passivating aqueous liquid composition according to the invention preferably, for reasons of economy of operation, is as short as possible, consist ⁇ ent with formation of a passivating layer as effective as desired. More specifically, the time of contact preferably is not more than, with increasing preference in the order given, s 200, 150, 100, 75, 50, 40, 30, 25, 20. 15, 13, 1 1 , 10, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.5, or 1.0 seconds.
- Spraying a heated working passivating aqueous liquid composition onto the surface to be passivated followed by removing excess liquid with a squeegee has been found effective in forming a passivated surface according to this invention within a few seconds at most.
- the surface to be passivated preferably is not rinsed with water or other diluent between contact with a working passivating aqueous liquid composition accord ⁇ ing to the invention and drying. Drying can be accomplished by simple exposure to am ⁇ bient air for a sufficient time, and indeed is preferably accomplished in this way if the passivated surface has been formed at a sufficiently high temperature that drying occurs 5 within a few seconds of separation from contact with the working passivating aqueous liquid composition according to the invention as described above.
- the passivating coating formed in a process according to the invention includes molybdenum in sufficient amounts to be detected by X-ray fluorescence.
- the coating is thick enough that the amount of molybdenum added-on during the passivation process, including drying after the contact with a working passivating aqueous liquid composition according to the invention corresponds to at least, with increasing prefer ⁇ ence in the order given, 1.0.
- molybdenum atoms 3.0, 5.0, 7.0, 9.0, 10.0, or 10.5 milligrams per square meter of the metal surface passivated (hereinafter usually abbreviated as "mg/m 2 "), measured as molybdenum atoms, and if very high corrosion resistance is needed more preferably is at least, with increasing preference in the order given, 12, 15, 20, 25, 30, or 32 mg/m 2 measured as molybdenum atoms and independently preferably, primarily for reasons of economy, corresponds to not more than 100, 75, 65, 55, 50, 45, 40, or 35 mg/m 2 mea- sured as molybdenum atoms.
- the amount of molybdenum added-on may conveniently be measured with a commercially available instrument, a PORTASPECTM Model 2501 X-ray spectrograph from Cianflone Scientific, or by other means known to those skilled in the art.
- the initial passivating layer After forming the initial passivating layer as described above, it is normally pre- ferred to further improve the corrosion and/or staining resistance of the passivated sur ⁇ face by overcoating it with a protective layer containing at least an organic binder.
- a protective layer containing at least an organic binder Any of a wide variety of clear and pigmented paints and like materials, as generally known per se in the art can be used for this purpose.
- a particularly useful type of overcoating for many purposes is a clear acrylic coating formed by drying into place a liquid layer of acrylic latex emulsion formed on the initially passivated surface.
- Such an overcoating preferably has a thickness after drying that is at least, with increasing preference in the order given, 0.2, 0.4, 0.6.
- ⁇ m 0.8, or 1.0 micrometres (hereinafter usually abbreviated as " ⁇ m") and independently preferably, primarily for reasons of economy, is not more than 10, 7, 5, 3, 2.5, 2.0, 1.5, or 1.3 ⁇ m.
- this relatively thin clear acrylic overcoating can serve adequately as the final coating layer in many in ⁇ stances.
- additional thicker coatings of paint and like materials adapted to a specific purpose as known er se in the art may be applied directly over this initial thin acrylic overcoating, or directly over the passivated metal surface itself.
- the substrate to be passivated is preferably thoroughly cleaned by any of various methods well known to those skilled in the art to be suitable for the particular substrate to be coated.
- the first four of the concentrate make-up compositions as described above were used to prepare working compositions that contained 10 % by volume of the liquid con- centrate make-up compositions.
- aqueous fluozirconic acid was also added to the working compositions, to produce the working composition concentrations shown in Table 3 below.
- Test panels of GALVALUMETM sheet which is steel sheet coated with an alloy of 55 % Al, 1.6 % Si, and 43.4 % Al and is a product of Bethlehem Steel Corporation, were cleaned in a cleaning solution prepared from PARCO® Cleaner 338, which is a commercial cleaner recommended for cleaning aluminiferous and zinciferous surfaces, is available from the Parker Amchem Division of Henkel Co ⁇ oration, Madison Heights, Michigan, USA, and was used according to the manufacturer's directions. The cleaned panels were then rinsed with water and subsequently immersed for a period of time noted below in a working composition according to the invention, which was maintained at a temperature of 49 to 54 °C, or in a comparison passivating composition as also described below.
- the passivated panels were then removed from contact with the passivating com ⁇ position and allowed to dry in ambient air. Drying was complete within 5 seconds.
- the thus passivated and dried surfaces were fur ⁇ ther coated with a mixture of 50 % each of RHOPLEXTM HA-16 and AC-73 acrylic latex emulsions. (These emulsions were commercially supplied by Rohm & Haas Company.)
- the thickness of the acrylic coating was controlled to be equivalent to 1.0 ⁇ 0.2 ⁇ m after drying, and the coating was then dried into place on the passivated surface without rins ⁇ ing. Panels were then physically tested. Some results are shown in Tables 4 and 5.
- This process which was not according to the invention, utilized a conventional prior art mixed hexavalent chromium and acrylic emulsion passivating process.
- the working composition according to the invention used for this process test was made in the same general manner as described above for other working compositions according to the invention, but it contained 12.1 g/L of PO 4 "3 ions from H 3 PO 4 used in making the corresponding concentrate make-up composition, 6.7 g/L of molybdenum, measured as its stoichiometric equivalent as MoO 3 , 1.7 g/L of starch, and no other ingredients except water, counterions, and reaction products of the four ingredients (i.e.. H-,0. H 3 PO 4 , MoO 3 , and starch mixed to make the concentrate.
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU15237/97A AU1523797A (en) | 1996-01-23 | 1997-01-15 | Passivation composition and process for coating |
AT97901312T ATE283116T1 (de) | 1996-01-23 | 1997-01-15 | Passivierungszusammensetzung und verfahren zum beschichten |
CA002242995A CA2242995C (en) | 1996-01-23 | 1997-01-15 | Passivation composition and process for zinciferous and aluminiferous surfaces |
EP97901312A EP0880410B1 (de) | 1996-01-23 | 1997-01-15 | Passivierungszusammensetzung und verfahren zum beschichten |
DE69731731T DE69731731T2 (de) | 1996-01-23 | 1997-01-15 | Passivierungszusammensetzung und verfahren zum beschichten |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/590,258 | 1996-01-23 | ||
US08/590,258 US5683816A (en) | 1996-01-23 | 1996-01-23 | Passivation composition and process for zinciferous and aluminiferous surfaces |
Publications (1)
Publication Number | Publication Date |
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WO1997027001A1 true WO1997027001A1 (en) | 1997-07-31 |
Family
ID=24361515
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/000012 WO1997027001A1 (en) | 1996-01-23 | 1997-01-15 | Passivation composition and process for coating |
Country Status (10)
Country | Link |
---|---|
US (1) | US5683816A (de) |
EP (1) | EP0880410B1 (de) |
JP (1) | JPH09202977A (de) |
AR (1) | AR005516A1 (de) |
AT (1) | ATE283116T1 (de) |
AU (1) | AU1523797A (de) |
DE (1) | DE69731731T2 (de) |
ES (1) | ES2232856T3 (de) |
WO (1) | WO1997027001A1 (de) |
ZA (1) | ZA97532B (de) |
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US5789360A (en) * | 1996-03-04 | 1998-08-04 | Samsung Electronics Co., Ltd. | Cleaning solution for use on a semiconductor wafer following chemical-mechanical polishing of the wafer and method for using same |
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US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
US10920324B2 (en) | 2012-08-29 | 2021-02-16 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
Also Published As
Publication number | Publication date |
---|---|
ATE283116T1 (de) | 2004-12-15 |
EP0880410A1 (de) | 1998-12-02 |
AU1523797A (en) | 1997-08-20 |
US5683816A (en) | 1997-11-04 |
EP0880410B1 (de) | 2004-11-24 |
AR005516A1 (es) | 1999-06-23 |
DE69731731T2 (de) | 2005-12-15 |
ES2232856T3 (es) | 2005-06-01 |
EP0880410A4 (de) | 1999-04-07 |
JPH09202977A (ja) | 1997-08-05 |
DE69731731D1 (de) | 2004-12-30 |
ZA97532B (en) | 1997-07-30 |
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